Carbonium ion Rearrangement:

Pinacol-pinacolone Rearrangement
Pinacol-pinacolone Rearrangement

 Conversion of an alcohol having two

adjacent OH groups (pinacol) to a ketone
(pinacolone) by the action of acid
 Mechanism
 Mechanism of the pinacol rearrangement of a
symmetrical glycol
CH3 CH3 CH3 CH3 _ OH CH3 CH
H2SO4 2 3
H3C CH3 H3C CH3 H3C +
OH OH OH OH2 OH CH3
+
1. Protonation of 2. Loss of water
pinacol a hydroxyl group
3. Methyl migration
4. Deprotonation
H3C CH3 H3C CH3 H3C CH3
+ CH3
CH3 _ + CH3 ..
O H H O+ H O
CH3 CH3 CH3
pinacolone Resonance-stablized carbocation
Facts
 1, 2 shift takes place in carbonium ion
which is already a tertiary carbonium ion
 Probably it is due to stabilization of
rearranged ion that is affected by
– delocalization involving the electron pair on
the oxygen atom, and
– readily loss of proton from the oxygen to
produce a stable end product
 Asymmetric glycol

+ +
Ph2C CH2 H Ph2C CH2
+
Ph2CH CH
OH OH OH
OH
Ph2CH CH +Ph2CH CH
+OH H
O

The stable cation formed is superior for

stabilization
Pinacol rearrangement of an asymmetrical
glycol
Me Ph Me
Ph O Me
H2SO4
HO OH HO + Ph
Me Ph Me Ph Me Ph
A B C

Me Ph
+ OH
Me Ph
D
Et Ph Et Ph O Et
H2SO4
HO OH HO + _ + Ph
Ph H
Et Ph Et Et Ph
E F
Bromohydrin to pinacolone
Hydroxyamine to pinacolone
Facts
 It seems that migration of alkyl group is
extremely fast on the loss of leaving group;
taking place simultaneously
 That migrating group is from the opposite
side of the leaving group
– Because rearrangement is much more easy in
compounds having trans configuration than that
having cis configuration
Which group
migrates?
H+ PhHC CHPh
PhHC CHPh
+
OH OH OH
+
Ph2CH CH Ph2CH CH + Ph2CH CH
+OH H
OH O

Phenyl group move first because of

greater chances of stabilization due to
delocalization
Which group
migrates?
 The steric chemistry of Pinacol-
pinacolone Rearrangements

It is found that o-MeOPh migrate

more than a 1000 time less readily
than p-substituent and even much
less than phenyl. This is due to
interference in the transition state
with non-migrating group
Solved problem
Explain the following experimental facts ：
R R R
R
R
C R +
H2SO4 O O
OH OH
(A) (B) (C)

When R=CH3, （ B ） and （ C ） are formed ；

When R=Ph, only （ C ） is formed.
When R=Me R R
+ C R
C R

+O H 2 OH OH
(1) (2)
R R
+
-H + C R
R C R
+H+ :O H O
C R
(3) (B)
OH OH
R R
(A) +
C R C R
+ OH2
OH
(4) OH (5)
R + R
-H
+ R R

:O H (6) O (C)
When R=Ph